Addition of chlorinated acetic acid derivatives to olefins



UNITED STATES PATENT OFFICE ADDITION OF CHLORINATED ACETIC ACIDDERIVATIVEQTO OLEFINS Morris 8. Kharasch and Wilbert H. Um, Chicago,

111., assignors to United States Rubber Comgany, New York, N. Y., acorporation of New ersey No Drawing. Application August 23, 1946,

Serial No. 692,734

4 Claims. (Cl. 260-408) This invention relates to the addition ofdeperoxide such as benzoyl peroxide, acetyl peroxrivatives ofa-halogenated carboxylic acids to oride, or we may use any peroxycompound which ganic compounds containing carbon-to-carbon decomposes togive free radicals, as for example, unsaturation. More particularly, itrelates to the ascaridol. tertiary butyl hydroperoxide, etc. addition ofchloro acetic acid chlorides or esters 5 The amount of chloro acidderivative used to oleflns containing at least three carbon atoms.should preferably be equal to at least one mole One object of thisinvention is to provide new for each mole of olefin used, although themolar and useful halogen-containing derivatives of orratio of halo acidto olefin may be increased conganic acids. Another object of thisinvention is sidera ly. sp al y where it is s d to r du toprovide amethod of preparing certain a-OhlOlO the y e of Polymeric a t P od o aaliphatic acid derivatives. minimum.

We have found that esters or chlorides of chloro on the -h O acidderivatives suitable for acetic acids add to organic compoundscontainthis invention are the chlorides and esters of the ing oleflnicunsaturation to form new and useful chlorinat d acet c aci s su h as. fr a l chlorine-substituted carboxylic acids when a mixtrichloro acetylchloride, methyl lu'ichloro acetate, ture of .the chloro acid derivativeand the oleflnic yl triehlOrO ac e, dichloro acetyl chlo i e. compoundis heated in the presence of ll methyl dichloro acetate, ethyl dichloroacetate, amount of a'diacyl peroxide or other peroxy com-11101100111011) acetyl de. m y monochloro pound capable of decomposingthermally to yield acetate, and ethyl monochloro acetate. In addifreeorganic radicals. tion to the methyl and ethyl esters mentioned- Inparticular, we have found the a-halo acid above, Other corresponding l yesters Such as derivatives as exemplified by the derivatives of prepyl.bu yl. l, ay be us d.

chlorinated acetic acids will add to oleflns to give Among the o flhydrocarbons n ni a excellent yield f t following types of least threecarbon atoms to which the chlorinated pounds: acetic acid derivativeswill add under the conditions of the present invention, the followingmay RCH=CHz+CHClzCOOCHsbe mentioned: propylene, butene-l, hexene-l,RCHzCHzCClzCOOCHs octene-l, and other unsaturated hydrocarbonsRCH=CH2+CChCOCHRCHClCHzCClzCOCI containing a terminal double bond. Loweryields V 0 of the desired addition products are obtained R is asaturated hydrocarbon radical. when the double bond in the unsaturatedcom- The temperature at which the reaction between pound is nonterminal,such as in hexene-3, octhe a-halo acid derivative and the oleflnic comtn -z, b tent-z. Finally, very poor yields of th pound is carried out isnot critical except that it desired compounds are obtained when ahydrogen should be high enough to cause decomposi ion of atom of theethylene molecule is replaced by an the pe y C mpo nd s d s t p omo Inaromatic group as in styrene, or vinyl naphthagenelal. temperatures inthe range f lene. In the case of these latter compounds only C.15 C. Wll be Satisfactory although h ghe or polymers are formed which containmany molelower e p a y be employed. if desiredcules of the unsaturatedcompound per molecule The time of heating is not critical and it iscusof t chlorinated acid halide or tto a y to continue the heating atleast until an In order not to extend unduly the number of appreciablequantity of he des ed addition P iexamples, the following fewillustrative examples uct is formed. The amount of the diacyl peroxideemployed of th1e mventmn are cited. may range from 1 to 20% by weight ofthe oleflnic Example 1 compound used although larger amounts may beused, if desired. As a rule, the yield of the de- P A i t e containing 2p ts of c -1 end sired product will depend upon the amount of 177 partsof methyl dichloro acetate is heated in promoter used, larger quantitiesgiving higher a flask for 4 hours at 100 C. in the presence of yieldsand conversely smaller quantities giv n 2 Parts of dietetyl per i e- Aut 57 p rts of somewhat smaller yields. The promoter may be additionproduct remains in the flask after readded at the start of the reactionor in increments moval of the starting materials at reduced presduringthe heating period. The latter method is sure. This material upondistillation gives 29 preferable in many cases. parts of a fractionwhich boils at 74-75 C. at

As a suitable promoter, we may use any diacyl 0.3 mm. pressure and has arefractive index Mol. weight n 2o=1.4561. This material is a halo acidderivative with the following properties:

Cl content per cent 28.17 255 The reaction may be represented asfollows:

The product is named methyl a;a-dichlorocaprate.

The calculated chlorine content of this compound is 27.85 and themolecular weight is 255. The structure of this compound was confirmed bywell established chemical procedures.

The residue is distilled in a molecular still and is found to be amixture of dimethyl tetrachloro succinate and the condensation productof two molecules of octene-l and one of methyl dichloro acetate.

Example 2 A better yield of the mono addition product and a smalleramount of the higher condensation products (two or more molecules ofoctene-l to one molecule of chlorinated acetic acid derivative) areobtained when 25 parts of octene-l and 180 parts of trichloro acetylchlorine are heated in a flask in the presence of 2 parts of diacetylperoxide and the reaction mixture worked up as in Example 1. Theaddition product obtained is u,a,'Y,-tIiOh10rO capryl chloride (B. P.123-42690. at 0.3 mm. n,, =1.4839) and the amount obtained correspondsto81% yield based on the octene used. The analysis of the product showsthe following:

Cl, 48.1%; mol. wt. 294. Calculated for CioHmOCh: Cl, 48.2%; mol. wt.294.

The structure of this compound was confirmed by well establishedchemical procedures.

4 Example 3 The condensation of methyl monochloro acetate and octene1under the same conditions as in Examples 1 and 2 gave 10% of an a-haloacid derivative based on the octene-l used.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. An adduct of a compound of the formula RCH=CH2 where R is a saturatedhydrocarbon radical in which the carbon atoms range from 1 to 6 and anacid chloride of a chloracetlc acid which contains two to threealpha-chlorine atoms. p

2. A method of forming addition products which comprises catalyticallyactivating with a peroxy compound catalyst a mix composed of an olefinof the formula RCH=CH2 where R is a saturated hydrocarbon radical inwhich the carbon atoms range from 1 to 6 and at least one molecularproportion of an acid chloride of a chloroacetic acid for each molecularproportion of the olefin.

. 3. Alpha,alpha,gamma-trichloro capryl chloride.

4. A method of forming alpha,alpha,gammatrichloro capryl chloride whichcomprises reacting octene-l with at least one molecular proportion oftrichloro acetyl chloride for each molecular proportion of -octene-1, inthe presence of a peroxy compound catalyst.

MORRIS S. KHARASCH. WILBERT H. URRY.

REFERENCES CITED The following references are of record in the file ofthis patent:

Servais, Recueil des travaux chim. des Pays- Bas," volume 20 (1901)pages 46-7.

Certificate of Correction Patent N 0. 2,471,570. May 31, 1949.

MORRIS S. KHARASCH ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows:

Column 2, line 33, for butent read butene; column 3, line 27, for theword chlorine read chloride; line 37, for Cl, 48.2% read Cl48.2%;

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 25th day of October, A. D. 1949.

THOMAS F. MURPHY,

Am'atant Oommz'saioner of Patents.

